Effervescent compositions and dry effervescent granules

ABSTRACT

The present invention discloses dry effervescent granules comprising an acid, carbonate source and optionally a binder, wherein said acid, carbonate source and optionally binder are in close physical proximity. The invention also discloses granular compositions, containing effervescence material comprising an acid and a carbonate source, which has an effervescence index (EI) of at least 50. The granular compositions may be obtainable by incorporating said pre-formed dry effervescent granules into said granular compositions, especially detergent compositions. Improved effervescence is obtained when diluting these granular detergent compositions with water to obtain a washing/soaking liquor, resulting thereby in improved dissolution/dispensing characteristic and improved stain removal performance on soiled fabrics.

TECHNICAL FIELD

The present invention is applicable to compositions which need to bedissolved in an aqueous medium in an easy and fast way. This technologymay found application in various fields, e.g., in detergent compositionslike laundry detergent compositions, soaking detergent compositions,dishwashing compositions or any other compositions for householdapplications, in pharmaceutical preparations, dental preparations, foodand the like. More particularly, the present invention relates togranular detergent compositions intended for the cleaning of fabrics.

BACKGROUND OF THE INVENTION

A problem associated to conventional granular compositions which are tobe used by the consumer after having been diluted typically with water,is their tendency towards poor dissolution. That tendency has beenexacerbated by the recent trend in for example the detergent industrytowards higher bulk density granular compositions and towards granulardetergent compositions which have a higher content of activeingredients. Granular detergent compositions of high bulk densitiesranging from 650 to 1100 kg/m3 are attractive to consumers but notsatisfactorily dissolved into an aqueous medium.

Another difficulty with detergent compositions is that they are noteasily flushed from the dispenser drawer of a washing machine. Similarproblems are encountered when using such granular detergent compositionsin a dosing device in the washing drum.

It is known to use citric acid and bicarbonate in powder compositions topromote dissolution of for example pharmaceutical preparations. In orderto ensure an uniform distribution of these effervescent materials inthese preparations it is essential to utilise sodium bicarbonate andcitric acid in the form of fine powders. It is also necessary toincorporate considerable proportions of these effervescent materials inthe preparations in order to obtain the desired effect. Furthermore, amajor issue with such powder compositions is the poor storage stabilitywhen they are exposed to moisture.

It is thus an object of the present invention to provide compositionswith improved dissolution and/or dispensing characteristics upondilution in an aqueous medium. It is a further object of the presentinvention that the effective dissolution characteristics of thecompositions of the present invention are not reduced or lost duringstorage.

It has now been found that these objects can be met by providing adetergent composition comprising effervescence material containing anacid and a carbonate source having a specific effervescence index.Preferably, the effervescence material or at least part thereof, iscomprised in a dry effervescence granule. In particular, it has beenfound that the objectives can thus be met by providing a granularcomposition obtainable by a process which comprises the step of firstforming a dry effervescent granule comprising an acid, carbonate and/orbicarbonate and optionally a binder wherein the acid, carbonate and/orbicarbonate and the binder are in close physical proximity, thenincorporating this granule in the granular composition. Indeed, it hasbeen found that for example the incorporation of such pre-formed dryeffervescent granules typically obtainable by dry-powder compaction orpressure agglomeration into the compositions according to the presentinvention provides improved dissolution and/or dispensingcharacteristics to all the active ingredients present in thecompositions and good storage stability in respect of the dissolutionpotential. It has been found that the compositions according to thepresent invention deliver enhanced effervescence which results inimproved dissolution or dispensing of the compositions, when thecompositions are contacted with water (i.e., in use conditions), ascompared to compositions having the same effervescence powders presentat the same levels, wherein all the effervescent materials are uniformlydistributed in the whole granular compositions, i.e., are two separategranular particles.

Another problem associated to conventional detergent is their tendencyof not always satisfactorily meeting consumer needs in respect to theperformance delivered by the active ingredients present in saidcompositions.

Furthermore, when formulating bleach-containing detergent compositions,comprising an oxygen bleach, it is not only desirable to delivereffective stain removal performance (e.g., on bleachable stains), butimportantly such compositions need also to be thermally stable uponprolonged storage time before their actual use.

It has now been found that these problems are solved by the detergentcompositions of the invention, as described herein. Furthermore, it hasbeen found that in a preferred embodiment of the present invention, thepresence of the pre-formed dry effervescent granules, as describedherein, in a detergent composition comprising an active detergentingredient, produces enhanced effervescence upon contact with water,which results in improved dissolution and/or dispensing of thecomposition and improved stain removal performance observed on thefabrics treated, as compared to the stain removal performance deliveredin the same conditions with compositions, having the same ingredients,at the same levels, which however comprise all the effervescentmaterials uniformly distributed in the whole granular compositions, orwith the same compositions but being free of any effervescent materials.More particularly, it has been found that the stain removal performanceis even more improved due to the presence of the dry pre-formedeffervescent granules, in a detergent composition. This has also beenfound when the composition is used in short soaking operations, i.e.when the soiled fabrics are immersed in a soaking liquor comprisingwater and said composition, simultaneously or immediately after itspreparation (e.g., before 5 minutes and more preferably before 1 minuteafter its preparation), for typically less than 30 minutes, before beingremoved from the soaking liquor. Advantageously, the stain removalperformance improvement associated to the detergent compositions of thepresent invention is also even more noticeable at low usagetemperatures, typically below 30° C.

Advantageously the improved stain removal performance is observed on avariety of stains including tough outdoor dirt like greasy stains (e.g.spaghetti sauce, bacon grease), enzymatic stains (blood), bleachablestains (grass) and/or particulate soils (mud/clay).

Another advantage of the present invention is that the stain removalperformance, when soaking/washing a fabric in presence of a detergentcomposition as described herein, is improved even in the presence ofrelatively high levels of hardness ions.

It has now been found that compositions of the invention and the drypre-formed effervescent granules are bleach-compatible and stable uponstorage.

SUMMARY OF THE INVENTION

The present invention provides a detergent composition comprising aeffervescence source, containing an acid and a carbonate source, wherebythe effervescence index of the composition is at least 10, as describedherein.

The present invention also encompasses a dry effervescent granulecomprising an acid, a carbonate source, preferably carbonate/bicarbonateand optionally a binder, wherein said acid, carbonate source andoptionally binder are in close physical proximity.

The present invention also encompasses a process of manufacturing thedry effervescent granules as described herein, wherein said processcomprises the steps of:

first mixing the acid, the carbonate source and optionally the bindertogether to obtain a mixture,

then submitting the mixture to a pressure agglomeration step, as definedherein, to obtain agglomerated mixture,

and finally submitting the agglomerated mixture to a granulation step.

The present invention also encompasses a composition obtainable by aprocess which comprises the step of first forming a dry effervescentgranule comprising an acid, a carbonate source, preferably carbonateand/or bicarbonate and optionally a binder wherein the acid, carbonatesource and optionally the binder are in close physical proximity, thenincorporating this granule in said composition. In a preferredembodiment compositions are granular or solid detergent compositionscomprising at least a detergent active ingredient, preferably at leastan oxygen bleach or a mixture thereof.

The present invention further encompasses the use of a dry effervescentgranule, as described herein, in a detergent composition, preferablysolid or granular, comprising at least one detergent active ingredient,for improved stain removal performance. This may typically be, whenfabrics are immersed, for an effective period of time, in a soakingliquor comprising water and an effective amount of said granulardetergent composition before removing said fabrics from said soakingliquor.

The present invention further encompasses the use of a dry effervescentgranule, as described herein, in a composition, preferably granular orsolid, comprising an oxygen bleach, preferably percarbonate and/orperborate, for improved thermal stability of said composition uponstorage.

Finally, the present invention also encompasses a process of soakingfabrics, wherein said fabrics are immersed in a soaking liquorcomprising water and an effective amount of a composition as describedherein, for an effective period of time, then removed from said soakingliquor and also encompasses a process of washing fabrics in a domesticwashing machine comprising, introducing into a dispensing device whichis placed in the drum of the washing machine, or introducing into thedispensing drawer of a washing machine, an effective amount of adetergent composition as described herein.

DETAILED DESCRIPTION OF THE INVENTION

The Dry Effervescent Granule and Process for its Manufacturing

The present invention encompasses a dry effervescent granule comprisingan acid, carbonate source, preferably carbonate and/or bicarbonate, andoptionally a binder wherein the acid, carbonate source and optionallythe binder are in close physical proximity and a process formanufacturing the same.

By “dry” it is to be understood that the granules are substantially freeof water, i.e., that no water has been added or present other than themoisture of the raw materials themselves. Typically, the level of wateris below 5% by weight of the total granule, preferably below 3% and morepreferably below 1.5%.

For the purpose of the present invention, the term close physicalproximity means that the effervescent materials, i.e., the acid, andcarbonate source, are in intimate admixture in the effervescent granulesand may not be separated by anything else than a binder, if the binderis present in the dry effervescent granule. Preferably, according to thepresent invention, at least part of the acid and the carbonate are notseparate discrete particles in the granular compositions.

The dry effervescent granules according to the present inventioncomprising the effervescent materials, i.e., the acid and the carbonatesource, in close physical proximity are preferably obtainable bydry-powder compaction or pressure agglomeration. While all bindingmechanisms can occur in pressure agglomeration, adhesion forces betweenthe solid particles, i.e., between the acid, carbonate source andoptionally the binder if present, play an especially important role.This is because pressure agglomeration, especially high pressureagglomeration, is an essentially dry process that forms new entities(i.e., dry effervescent granules) from solid particles (i.e., the acid,bicarbonate, carbonate source and optionally the binder) by applyingexternal forces to densify a more or less defined bulk mass or volumeand create binding mechanisms between the solid particles providingstrength to the new entity, i.e. the high external force applied bringsthe solid particles closely together.

The dry effervescent particles results in a very fast carbon dioxideproduction and therefore in accelerated dispersibility and dissolutionrate of the granular composition. The granular compositions of thepresent invention, as described herein, comprising the dry effervescentgranules allow dispensing and dissolution in water of the granularcompositions in a shorter period of time and at lower total level ofeffervescent particles/materials and ensure a faster and more effectivedelivery of detergent ingredients to the wash.

Suitable acids to be used herein include solid organic, mineral orinorganic acids, salts or derivatives thereof or a mixture thereof. Itmay be preferred that the acids are mono-, bi- or tri-protonic acids.Such acids include mono- or polycarboxylic acids preferably citric acid,adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid,tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid,malonic acid. Such acids are preferably used in their acidic forms, andit may be preferred that their anhydrous forms are used, or mixturesthereof. Derivatives also include ester of the acids. Surprisingly, ithas now been found that by using tararic, maleic and in particular malicacid as the acid in the dry effervescent granules, said granules deliverimproved physical and/or chemical stability upon prolonged storageperiods. When citric acid is used it may be preferred that its level iskept below 20% in the dry effervescent granules according to the presentinvention, in particular to facilitate processability and to allowappropriate storage stability of the granules.

The acid is preferably present in the dry effervescent granulesaccording to the present invention at a level of from 0.1% to 99% byweight of the total granule, preferably from 3% to 75%, more preferablyfrom 5% to 60% and most preferably from 15% to 50%.

In accordance with the present invention, 80% or more of the acid sourcepreferably has a particle size in the range of from about 150 microns toabout 1200 or even 1000 or even 710 microns.

Another essential feature of the present invention is a carbonatesource, including carbonate, bicarbonate and percarbonate salts, inparticular bicarbonate and/or carbonate. Suitable carbonates to be usedherein include carbonate and hydrogen carbonate of potassium, lithium,sodium, and the like amongst which sodium and potassium carbonate arepreferred. Suitable bicarbonates to be used herein include any alkalimetal salt of bicarbonate like lithium, sodium, potassium and the like,amongst which sodium and potassium bicarbonate are preferred.Bicarbonate may be preferred to carbonate, because it is more-weigheffective, i.e., at parity weigh bicarbonate is a larger CO₂ “reservoir”than carbonate. However, the choice of carbonate or bicarbonate ormixtures thereof in the dry effervescent granules may be made dependingon the pH desired in the aqueous medium wherein the dry effervescentgranules are dissolved. For example where a relative high pH is desiredin the aqueous medium (e.g., above pH 9.5) it may be preferred to usecarbonate alone or to use a combination of carbonate and bicarbonatewherein the level of carbonate is higher than the level of bicarbonate,typically in a weight ratio of carbonate to bicarbonate from 0.1 to 10,more preferably from 1 to 5 and most preferably from 1 to 2.

The carbonate source is preferably present in the dry effervescentgranules according to the present invention at a level of from 0.1% to99% by weight of the total, preferably from 30% to 95%, more preferablyfrom 45% to 85% and most preferably from 50% to 80%.

In accordance with the present invention, 80% or more of the carbonatesource preferably has a particle size in the range of from about 50microns to about 1200 or even from 150 to 1000 microns.

For optimum effervescence in aqueous medium the weight ratio of acid tocarbonate and/or bicarbonate in the dry effervescent granules is from0.1 to 10, preferably from 0.5 to 2.5 and more preferably from 1 to 2.

The diameter size of the dry effervescent granules of the presentinvention are preferably from 0.001 mm to 7 mm, preferably less than 2mm.

The diameter size as defined herein can be determined by sieving asample of the granules into a number of fractions (typically 5fractions) on a series of sieves, with mazes of various diameter oraperture size. The mean diameter size of the granules can be calculatedby plotting the weight fractions, obtained by the sieving, against theaperture size of the sieves. The mean particle size is taken to be theaperture size through which 50% by weight of the sample would pass.

The bulk density of the dry effervescent granules of the presentinvention is preferably from 500 g/l to 1200 g/l, more preferably from700 g/l to 1100 g/l.

The dry effervescent granules of the present invention may optionallycomprise a binder or a mixture thereof. Typically, the dry effervescentgranules comprise up to 50 % by weight of the total granule of a binderor a mixture thereof, preferably up to 35% and more preferably up to20%. Suitable binders to use herein are those known to those skilled inthe art and include anionic surfactants like C6-C20 alkyl or alkylarylsulphonates or sulphates, preferably C8-C20 alkylbenzene sulphonates,cellulose derivatives such as carboxymethylcellulose and homo- orco-polymeric polycarboxylic acid or their salts, nonionic surfactants,preferably C10-C20 alcohol ethoxylates containing from 5-100 moles ofethylene oxide per mole of alcohol and more preferably the C15-C20primary alcohol ethoxylates containing from 20-100 moles of ethyleneoxide per mole of alcohol. Of these tallow alcohol ethoxylated with 25moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles ofethylene oxide per mole of alcohol (TAE50) are preferred. Otherpreferred binders include the polymeric materials likepolyvinylpyrrolidones with an average molecular weight of from 12 000 to700 000 and polyethylene glycols with an average weight of from 600 to10 000. Copolymers of maleic anhydride with ethylene, methylvinyl ether,methacrylic acid or acrylic acid are other examples of polymericbinders. Others binders further include C10-C20 mono and diglycerolethers as well as C10-C20 fatty acids. In the embodiment of the presentinvention where a binder is desired C8-C20 alkylbenzene sulphonates areparticularly preferred.

In a preferred embodiment the granules according to the presentinvention consists of an acid, carbonate source and optionally a binder,wherein the acid, carbonate source and optionally the binder are inclose physical proximity.

The present invention further encompasses a process for manufacturingthe dry effervescent granules of the present invention comprising anacid, carbonate source and optionally a binder, wherein the acid,carbonate source and optionally the binder are in close physicalproximity. This process preferably comprises the steps of:

first mixing the acid, carbonate source and optionally the binder toform a mixture,

then submitting the mixture to a, preferably pressure, agglomerationstep to form a agglomerate mixture,

and finally granulation of the agglomerate mixture in a granulation stepso as to obtain said granules.

According to this process the effervescent raw materials and optionallythe binder if present are first mixed together without the addition ofwater and/or moisture apart those coming from the raw materialsthemselves so as to obtain a dry free flowing powder mixture. Then thisdry free flowing powder mixture comprising the effervescent particles(i.e. the acid and carbonate source), and optionally the binderparticles if present, undergoes a pressure agglomeration step,, i.e. adry process step wherein this free flowing powder mixture undergoes highexternal forces that bring the particles closely together therebydensifying the bulk mass of said particles and creating bindingmechanisms between the solid effervescent particles and the binder ifpresent. Indeed, pressure agglomeration results in an aggregationmechanism which is characterised by the presence of inter particlesbonds between primary solid effervescent particles and a structure inwhich these effervescent particles are still identifiable and retainmany of their characteristics, e.g. the ability to react together inpresence of water to deliver carbon dioxide.

The increase of density associated to the preparation of the dryeffervescent granules of the present invention obtainable by pressureagglomeration is closely linked to the pressure applied. Typically, thebulk density will increase up to 200 g/l, preferably from 10 g/l to 150g/l, starting from the density of the mixture comprising theeffervescent raw materials, i.e., acid and the carbonate source, andoptionally the binder, before having undergone a pressure agglomeration.

Pressure agglomeration may be carried out using different processeswhich can be classified by the level of forces applied. A preferredprocess to be used herein is roller compaction. In this process theacid, bicarbonate and/or carbonate and optionally the binder afterhaving been mixed together are forced between two compaction rolls thatapplies a pressure to said mixture so that the rotation of the rollstransforms the mixture into a compacted sheet/flake. This compactedsheet/flake is then granulated.

Typical roller compactors for use herein is for example PharmapaktorL200/50P® commercially available from Hosokawa Bepex GmbH. The processvariables during the pressure agglomeration step via roller compactionare the distance between the rolls, the feed rate, the compactionpressure and the roll speed. Typical feeding device is a feed screw. Thedistance between the rolls is typically from 0.5 cm to 10 cm, preferablyfrom 3 to 7 cm, more preferably from 4 to 6 cm. The pressing force istypically between 20 kN and 120 kN, preferably from 30 kN to 100 kN,more preferably from 40 kN to 80 kN. Typically, the roll speed isbetween 1 rpm and 180 rpm, preferably from 2 rpm to 50 rpm and morepreferably from 2 rpm to 35 rpm. Typically, the feed rate is between 1rpm and 100 rpm, preferably from 5 rpm to 70 rpm, more preferably from 8rpm to 50 rpm. Temperature at which compaction is carried out is notrelevant, typically it varies from 0° C. to 40° C.

By “granulation step” it is meant that the resulting mixture afterhaving undergone a pressure agglomeration step is cut into granules ofthe required length and rounded to obtain round or spherical granulesaccording to the diameter size as defined herein before. In thepreferred embodiment one way to carry out the granulation step after theroller compaction step is to mill the compacted flake/sheet. Milling maytypically be carried out with a Flake Crusher FC 200® commerciallyavailable from Hosokawa Bepex GmbH.

Depending on the end diameter size desired for the dry effervescentgranules the milled material may further be sieved. Such a sieving ofthe dry effervescent granules can for example be carried out with acommercially available Alpine Airjet Screen®.

Detergent Compositions

The present invention relates in one embodiment to a detergentcomposition comprising effervescence material, containing an acid and acarbonate source, whereby the acid and carbonate source are present in agranule together and/or the acid and the carbonate source are separatedpresent in the composition, characterised in that the EffervescenceIndex (EI) is at least 10, or even at least 15, the Effervescence Index(EI) being${EI} = {\frac{\left( {L \times S \times 100} \right)}{M} \times \left( {{NC}_{inter} + {NC}_{intra}} \right)}$

wherein L is the number of acidic groups of the acid having a pKa ofless or equal to 6, S is$\sqrt[3]{\left( {{{solubility}\quad {in}\quad {water}\quad {of}\quad {the}\quad {acid}\quad {in}\quad {g/{litre}}},{{at}\quad 25{^\circ}\quad {C.}}} \right)},$

M is the molecular weight of the acid, NC_(inter) is the density ofcontact points between the carbonate source and acid which are separatedpresent in the composition per mm³, and NC_(intra) is (the weightfraction of the acid in said granule)×(the weight fraction of thecarbonate source in said granule)×12.

The NC_(intra) and NC_(inter) can be calculated according the method asset out in: T Tanaka and N Ouchiyama, Ind. Chem. Fundam., 1980, 19,338-340.

The NC_(intra) is believed to represent the density of contact pointsbetween the acid and the carbonate source which are present in the samegranule, per mm³.

The compositions of the invention provide improved, efficienteffervescence when the EI is at least 10.

The granular compositions of the present invention, as described herein,comprising the dry effervescent granules allow dispensing anddissolution in water of the granular compositions in a shorter period oftime and at lower total level of effervescent particles/materials andensure a faster and more effective delivery of detergent ingredients tothe wash.

The compositions are preferably granular detergent compositions. Whenused herein, granular compositions include any composition which is inthe form of granules, tablets, bars, flakes, extrudates, etc.

The compositions of the invention preferably comprise a dryeffervescence granule, as described herein, comprising the acid and thecarbonate source or part thereof. It may be preferred that all the acidof the composition, is comprised in the dry effervescence granule.Alternatively, it may be preferred that the composition comprises a dryeffervescence granule and a dry-added acid and a dry-added carbonatesource, preferably less than 10% by weight of acid, more preferably lessthan 8% or even less than 5% by weight.

The composition is preferably obtainable by a process which comprisesthe step of first forming a dry effervescent granule comprising an acid,carbonate source and optionally a binder wherein the acid, carbonatesource and the binder are in close physical proximity, as describedherein, and then addition of this granule to the other detergentingredients of the composition.

The granular compositions of the present invention can be prepared withdifferent bulk densities, preferably being from 500 to 1200 g/l,preferably from 750 to 1050 g/l. These compositions can be made by avariety of methods well known in the art, including dry-mixing, spraydrying, agglomeration and granulation and combinations thereof.

In a preferred embodiment, the compositions, comprises from 0.1% to 99%by weight of the total composition of the dry effervescent granule,preferably from 2% to 50%, whereby soaking compositions preferablycomprise of from 5% to 40% and most preferably from 15% to 35% byweight, and automatic laundry or dishwashing compositions preferablyfrom 3% to 25%, more preferably from 4% to 15% by weight.

Additional Ingredients

The compositions according to the present invention typically compriseat least one active ingredient on top of said dry effervescent granules.In a preferred embodiment where the granular compositions according tothe present invention are granular detergent compositions, they compriseat least an active detergent ingredient or a mixture thereof. Typically,the granular detergent compositions comprise from 0.1% to 99% by weightof the total composition of an active detergent ingredient or a mixturethereof, preferably from 1% to 80% and more preferably from 5% to 70%.By “active detergent ingredient” it is meant any ingredient known tothose skilled in the art to provide a cleaning and/or bleaching benefitincluding for example surfactants, bleaches, enzymes, polymers,brighteners, builders, bleach activators, surfactants, alkali metal saltof silicate, chelating agents, fillers, soil suspending agents,dispersants, soil release agents, photoactivated bleaches such as Znphthalocyanine sulphonate, dyes, dye transfer inhibitors, pigments,perfumes, suds suppressors, clay softening system, cationic fabricsoftening agents, and mixtures thereof. Depending on the end useintended different mixtures of ingredients and levels may be used.

In a preferred embodiment of the present invention the granularcompositions comprise an oxygen bleach or a mixture thereof. Indeed,oxygen bleaches provide a multitude of benefits such as bleaching ofstains, deodorization, as well as disinfectancy. The oxygen bleach inthe granular compositions of the present invention may come from avariety of sources such as hydrogen peroxide or any of the additioncompounds of hydrogen peroxide, or organic peroxyacid, or mixturesthereof. By addition compounds of hydrogen peroxide it is meantcompounds which are formed by the addition of hydrogen peroxide to asecond chemical compound, which may be for example an inorganic salt,urea or organic carboxylate, to provide the addition compound. Examplesof the addition compounds of hydrogen peroxide include inorganicperhydrate salts, the compounds hydrogen peroxide forms with organiccarboxylates, urea, and compounds in which hydrogen peroxide isclathrated.

Examples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, peroxymonopersulfate and persilicate salts. The inorganicperhydrate salts are normally the alkali metal salts. The alkali metalsalt of percarbonate, perborate, or mixtures thereof, are the preferredinorganic perhydrate salts for use herein. Preferred alkali metal saltof percarbonate is sodium percarbonate, which may also be or be presentin the carbonate source. Preferred perborate is sodium perborate in theform of the monohydrate or tetrahydrate, respectively of nominal formulaNaBO₂H₂O₂ and NaBO₂H₂O₂.3H₂O. Other suitable oxygen bleaches includepersulphates, particularly potassium persulphate K₂S₂O₈ and sodiumpersulphate Na₂S₂O₈.

Typically, the granular compositions in the present invention compriseup to 90% by weight of the total composition of an oxygen bleach ormixtures thereof, preferably from 2% to 45% and more preferably from 10%to 40%.

It has now surprisingly been found that in the embodiment of the presentinvention wherein the granular compositions comprises at least an oxygenbleach as the active ingredient and the dry effervescent granules, thethermal stability of the granular composition upon prolonged storage isimproved.

Thus, in a broadest aspect, the present invention also encompasses theuse of such a dry effervescent granule as defined herein before, in agranular composition comprising an oxygen bleach, preferablypercarbonate and/or perborate, for improved thermal stability of saidcomposition upon storage.

Bleach Activators

Preferably the granular compositions herein further comprise a bleachactivator or a mixture thereof up to 30% by weight of the totalcomposition. Examples of suitable compounds of this type are disclosedin British Patent GB 1 586 769 and GB 2 143 231. Preferred examples ofsuch compounds are tetracetyl ethylene diamine, (TAED), sodium 3, 5, 5trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid asdescribed for instance in U.S. Pat. No. 4,818,425 and nonylamide ofperoxyadipic acid as described for instance in U.S. Pat. No. 4,259,201and n-nonanoyloxybenzenesulphonate (NOBS), and acetyl triethyl citrate(ATC) such as described in European patent application 91870207, 7e-Pthalimidoperoxyhexanoic acid (PAP), Phenolsulphonate Ester ofN-nonanoyl-6-aminocaproic acid, aliphatic diacyl peroxide (DAP) havingthe general formula R—C(O)—O—O—(O)C—R1, wherein R and R1 can be the sameor different and are linear or branched aliphatic groups having from 6to 20 carbon atoms. Also particularly preferred are N-acyl caprolactamselected from the group consisting of substituted or unsubstitutedbenzoyl caprolactam, octanyl caprolactam, nonanoyl caprolactam, hexanoylcaprolactam, decanoyl caprolactam, undecenoyl caprolactam, formylcaprolactam, acetyl caprolactam, propanoyl caprolactam, butanoylcaprolactam pentanoyl caprolactam. The granular compositions herein maycomprise mixtures of said bleach activators. Amide substituted alkylperoxyacid precursors.

Amide substituted alkyl peroxyacid precursor compounds are suitableherein, including those of the following general formulae:

wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is analkylene group containing from 1 to 14 carbon atoms, and R⁵ is H or analkyl group containing 1 to 10 carbon atoms and L can be essentially anyleaving group. Amide substituted bleach activator compounds of this typeare described in EP-A-01 70386.

A highly preferred bleach activator is nonanamido caproyl oxybenzenesulfonate, preferably in the form of the sodium salt (NACA-OBS).

Preferred mixtures of bleach activators herein comprisen-nonanoyloxybenzenesulphonate and/or nonanamido caproyl oxybenzenesulfonate together with a second bleach activator having a low tendencyto generate diacyl peroxide, but which delivers mainly peracid. Saidsecond bleach activators may include tetracetyl ethylene diamine (TAED),acetyl triethyl citrate (ATC), acetyl caprolactam, benzoyl caprolactamand the like, or mixtures thereof. Indeed, it has been found thatmixtures of bleach activators comprising n-nonanoyloxybenzenesulphonateand said second bleach activators, contribute to further boostparticulate soil removal performance while exhibiting at the same timegood performance on diacyl peroxide sensitive soil (e.g., beta-carotene)and on peracid sensitive soil (e.g., body soils).

Accordingly, the granular compositions herein may comprise from 0% to15% by weight of the total composition of NOBS or NACA-OBS, preferablyfrom 1% to 10% and more preferably from 3% to 7% and from 0% to 15% byweight of the total composition of said second bleach activatorpreferably from 1% to 10% and more preferably from 3% to 7%.

Surfactants

The granular compositions of the present invention may comprise asurfactant or a mixture thereof. Such surfactants may be desirable asthey contribute to deliver effective stain removal performance onvarious stains including greasy stains, enzymatic stains, particulatesoils and the like. Such surfactants may be present in the compositionsaccording to the present invention, in amounts up to 50% by weight ofthe total composition, preferably of from 1% to 30% and more preferablyof from 5% to 20%. Surfactants to be used herein include nonionicsurfactants, anionic surfactants, cationic surfactants, amphotericsurfactants, zwitterionic surfactants, and mixtures thereof.

Anionic Surfactants

Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates arecontemplated herein. Specific examples of substituted ammonium cationsinclude methyl-, dimethyl-, trimethyl-ammonium and quaternary ammoniumcations, such as tetramethyl-ammonium, dimethyl piperdinium and cationsderived from alkanolamines such as ethylamine, diethylamine,triethylamine, mixtures thereof, and the like. Exemplary surfactants areC₁₂-C₁₈ alkyl polyethoxylate (1.0) sulfate, C₁₂-C₁₈E(1.0)M), C₁₂-C₁₈alkyl polyethoxylate (2.25) sulfate, C₁₂-C₁₈E(2.25)M), C₁₂-C₁₈ alkylpolyethoxylate (3.0) sulfate C₁₂-C₁₈E(3.0), and C₁₂-C₁₈ alkylpolyethoxylate (4.0) sulfate C₁₂-C₁₈E(4.0)M), wherein M is convenientlyselected from sodium and potassium.

Other anionic surfactants useful for detersive purposes can also be usedherein. These can include salts (including, for example, sodium,potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of soap, C₉-C₂₀ linearalkylbenzenesulfonates, C₈-C₂₄ olefinsulfonates, sulfonatedpolycarboxylic acids prepared by sulfonation of the pyrolyzed product ofalkaline earth metal citrates, e.g., as described in British patentspecification No. 1,082,179, C₈-C₂₄ alkylpolyglycolethersulfates(containing up to 10 moles of ethylene oxide); alkyl ester sulfonatessuch as C₁₄₋₁₆ methyl ester sulfonates; acyl glycerol sulfonates, fattyoleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,alkyl phosphates, isethionates such as the acyl isethionates, N-acyltaurates, alkyl succinamates and sulfosuccinates, monoesters ofsulfosuccinate (especially saturated and unsaturated C₁₂-C₁₈ monoesters)diesters of sulfosuccinate (especially saturated and unsaturated C₆-C₁₄diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such asthe sulfates of alkylpolyglucoside (the nonionic nonsulfated compoundsbeing described below), branched primary alkyl sulfates, alkylpolyethoxy carboxylates such as those of the formulaRO(CH₂CH₂O)_(k)CH₂COO—M⁺ wherein R is a C₈-C₂₂ alkyl, k is an integerfrom 0 to 10, and M is a soluble salt-forming cation. Resin acids andhydrogenated resin acids are also suitable, such as rosin, hydrogenatedrosin, and resin acids and hydrogenated resin acids present in orderived from tall oil. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). Avariety of such surfactants are also generally disclosed in U.S. Pat.No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23,line 58 through Column 29, line 23 (herein incorporated by reference).

Other anionic surfactants suitable to be used herein may also includethose according to the formula R—SO3M, wherein R is a substituted orunsubstituted, saturated or unsaturated, linear or branched hydrocarbonchain having from 6 to 40 carbon atoms and M is H or a cation.Preferably R is a substituted or unsubstituted, saturated orunsaturated, linear or branched alkyl group having from 6 to 40 carbonatoms, preferably from 8 to 30, more preferably from 10 to 25 and mostpreferably from 12 to 18. Preferably M is a cation which can be forexample a metal cation (e.g., sodium, potassium, lithium, calcium,magnesium etc), ammonium or substituted-ammonium (e.g., methyl-,dimethyl-, and trimethyl ammonium cations and quaternary ammoniumcations, such as tetramethyl-ammonium and dimethyl piperdinium cationsand quaternary ammonium cations derived from alkylamines such asethylamine, diethylamine, triethylamine and mixtures thereof and thelike). Suitable anionic sulphonates to used herein are sodium paraffinsulphonate. They may be commercially available from Hoescht under thename of Hostapur® or Hostatat®.

Nonionic Surfactants

Suitable nonionic surfactants to be used herein are typicallyalkoxylated nonionic surfactants according to the formula RO—(A)_(n)H,wherein R is a substituted or unsubstituted, saturated or unsaturated,linear or branched hydrocarbon chain having from 6 to 40 carbon atoms, Ais an alkoxy group having from 2 to 10 carbon atoms, and wherein n is aninteger from 9 to 100, or a mixture thereof.

Preferably R is a substituted or unsubstituted, saturated orunsaturated, linear or branched alkyl group or aryl group having from 6to 40 carbon atoms, preferably from 8 to 25, more preferably from 12 to20. Typical aryl groups include the C12-C18 alkyl benzene groups.Preferably n is an integer from 9 to 100, more preferably from 10 to 80and most preferably from 10 to 30. A preferably is an alkoxy grouphaving from 2 to 8 carbon atoms, preferably from 2 to 5 and morepreferably is propoxy and/or ethoxy.

Accordingly suitable alkoxylated nonionic surfactants for use herein areDobanol® 91-10 (R is a mixture of C₉ to C₁₁ alkyl chains, A is ethoxy, nis 10) Luthensol AT® or AO® surfactants (where R is a mixture of linearC16 to C18 alkyl chain or unbranched C13-C15, A is ethoxy, and n can be11, 18, 25, 50 or 80), or mixtures thereof. These Dobanol® surfactantsare commercially available from SHELL, while the Luthensol® surfactantsare available from BASF.

Suitable chemical processes for preparing the alkoxylated nonionicsurfactants for use herein include condensation of correspondingalcohols with alkylene oxide, in the desired proportions. Such processesare well known to the man skilled in the art and have been extensivelydescribed in the art.

Such highly alkoxylated nonionic surfactants are particularly suitableto be used herein as they deliver improved particulate stains removalperformance. Indeed, it is speculated that they act a soil suspendingagent, i.e. they allow suspension of particulate soils and prevent/avoidthe redeposition of said soils.

Other suitable surfactants to be used herein are sorbitan estersaccording to the formula C₆H₉O₂ (C₂H₄O)_(x) R₁R₂R₃, wherein x is aninteger of from 0 to 40, R₁, R₂ are independently OH or(C_(n)H_(2n+1))COO, and R₃ is (C_(n)H_(2n+1))COO group, where n is aninteger of from 11 to 17.

In the preferred compositions herein, x is 0 or 20, and the mostpreferred compositions herein comprise polyethoxylated (20) sorbitantristearate, i.e. C₆H₉O₂ (C₂H₄O)₂₀ (C₁₇H₃₅COO)₃, or polyethoxylated (20)sorbitan monostearate, i.e. C₆H₉O₂(C₂H₄O)₂₀(OH)₂(C₁₇H₃₅COO), or sorbitanmonostearate, i.e. C₆H₉O₂(OH)₂(C₁₇H₃₅COO), or sorbitan monopalmitate,i.e. C₆H₉O₂(OH)₂(C₁₅H₃₁COO), or mixtures thereof. All these materialsare commercially available under several trade names, such asGlycosperse TS 20 from Lonza (polyethoxylated sorbitan tristearate),Glycosperse S 20 from Lonza (polyethoxylated sorbitan monostearate),Radiasurf 7145 from Fina (sorbitan monostearate), Radiasurf 7135 fromFina (sorbitan monopalmitate), Armotan MP from Akzo (sorbitanmonopalmitate). It has further been found that combining ethoxylatedsorbitan esters with non-ethoxylated sorbitan esters provides betterperformance than either kind alone.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2MConc. manufactured by Miranol, Inc., Dayton, N.J.

Polyhydroxy fatty acid amides suitable for use herein are those havingthe structural formula R²CONR¹Z wherein: R1 is H, C₁-C₄ hydrocarbyl,2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixturethereof, preferable C1-C4 alkyl, more preferably C₁ or C₂ alkyl, mostpreferably C₁ alkyl (i.e., methyl); and R₂ is a C₅-C₃₁ hydrocarbyl,preferably straight-chain C₅-C ₁₉ alkyl or alkenyl, more preferablystraight-chain C₉-C₁₇ alkyl or alkenyl, most preferably straight-chainC₁₁-C₁₇ alkyl or alkenyl, or mixture thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z is a glycityl.

Suitable fatty acid amide surfactants include those having the formula:R⁶CON(R⁷)₂ wherein R⁶ is an alkyl group containing from 7 to 21,preferably from 9 to 17 carbon atoms and each R⁷ is selected from thegroup consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, and—(C₂H₄O)_(x)H, where x is in the range of from 1 to 3.

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from 6 to 30 carbon atoms and a polysaccharide, e.g., apolyglycoside, hydrophilic group containing from 1.3 to 10 saccharideunits.

Preferred alkylpolyglycosides have the formula

R²O(C_(n)H_(2n)O)t(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived fromglucose.

Suitable amine oxides include those compounds having the formulaR³(OR⁴)_(x)N⁰(R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl,acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containingfrom 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene groupcontaining from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to5, preferably from 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl groupcontaining from 1 to 3, or a polyethylene oxide group containing from 1to 3 ethylene oxide groups. Preferred are C₁₀-C₁₈ alkyl dimethylamineoxide, and C₁₀₋₁₈ acylamido alkyl dimethylamine oxide.

Cationic Surfactant

A cationic surfactant may be comprised in the surface active componentof the composition of the invention, preferably be present at a level offrom 0.5% to 80% by weight of the component, more preferably from 1% to60%, most preferably from 3% to 50% by weight of the component.

Preferably the cationic surfactant is selected from the group consistingof cationic ester surfactants, cationic mono-alkoxylated aminesurfactants, cationic bis-alkoxylated amine surfactants and mixturesthereof.

Cationic mono-alkoxylated Amine Surfactants

The optional cationic mono-alkoxylated amine surfactant for use herein,has the general formula:

wherein R¹ is an alkyl or alkenyl moiety containing from about 6 toabout 18 carbon atoms, preferably 6 to about 16 carbon atoms, mostpreferably from about 6 to about 11 carbon atoms; R² and R³ are eachindependently alkyl groups containing from one to about three carbonatoms, preferably methyl; R⁴ is selected from hydrogen (preferred),methyl and ethyl, X⁻ is an anion such as chloride, bromide,methylsulfate, sulfate, or the like, to provide electrical neutrality; Ais selected from C₁-C₄ alkoxy, especially ethoxy (i.e., —CH₂CH₂O—),propoxy, butoxy and mixtures thereof; and p is from 1 to about 30,preferably 1 to about 15, most preferably 1 to about 8.

Highly preferred cationic mono-alkoxylated amine surfactants for useherein are of the formula

wherein R¹ is C₆-C₁₈ hydrocarbyl and mixtures thereof, preferablyC₆-C₁₄, especially C₆-C₁₁ alkyl, preferably C₈ and C₁₀ alkyl, and X isany convenient anion to provide charge balance, preferably chloride orbromide.

As noted, compounds of the foregoing type include those wherein theethoxy (CH₂CH₂O) units (EO) are replaced by butoxy, isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

Cationic bis-alkoxylated Amine Surfactant

The cationic bis-alkoxylated amine surfactant for use herein, has thegeneral formula:

wherein R¹ is an alkyl or alkenyl moiety containing from about 6 toabout 18 carbon atoms, preferably 6 to about 16 carbon atoms, morepreferably 6 to about 11, most preferably from about 8 to about 10carbon atoms; R² is an alkyl group containing from one to three carbonatoms, preferably methyl; R³ and R⁴ can vary independently and areselected from hydrogen (preferred), methyl and ethyl, X⁻ is an anionsuch as chloride, bromide, methylsulfate, sulfate, or the like,sufficient to provide electrical neutrality. A and A′ can varyindependently and are each selected from C₁-C₄ alkoxy, especiallyethoxy, (i.e., —CH₂CH₂O—), propoxy, butoxy and mixtures thereof; p isfrom 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30,preferably 1 to about 4, and most preferably both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for useherein are of the formula

wherein R¹ is C₆-C₁₈ hydrocarbyl and mixtures thereof, preferably C₆,C₈, C₁₀, C₁₂, C₁₄ alkyl and mixtures thereof. X is any convenient anionto provide charge balance, preferably chloride. With reference to thegeneral cationic bis-alkoxylated amine structure noted above, since in apreferred compound R¹ is derived from (coconut) C₁₂-C₁₄ alkyl fractionfatty acids, R² is methyl and ApR³ and A′qR⁴ are each monoethoxy.

Other cationic bis-alkoxylated amine surfactants useful herein includecompounds of the formula:

wherein R¹ is C₆-C₁₈ hydrocarbyl, preferably C₆-C₁₄ alkyl, independentlyp is 1 to about 3 and q is 1 to about 3, R² is C₁-C₃ alkyl, preferablymethyl, and X is an anion, especially chloride or bromide.

Other compounds of the foregoing type include those wherein the ethoxy(CH₂CH₂O) units (EO) are replaced by butoxy (Bu) isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

The surfactants may also include a cationic ester surfactant. That is, apreferably water dispersible compound having surfactant propertiescomprising at least one ester (ie —COO—) linkage and at least onecationically charged group. Suitable cationic ester surfactants,including choline ester surfactants, have for example been disclosed inU.S. Pat. Nos 4,228,042, 4,239,660 and 4260529.

Preferred cationic ester surfactants are those having the formula:

wherein R₁ is a C₅-C₃₁ linear or branched alkyl, alkenyl or alkarylchain or M⁻.N⁺(R₆R₇R₈)(CH₂)_(s); X and Y, independently, are selectedfrom the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONHand NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH orNHCOO group; R₂, R₃, R_(4,) R₆, R₇, and R₈ are independently selectedfrom the group consisting of alkyl, alkenyl, hydroxyalkyl,hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; andR₅ is independently H or a C₁-C₃ alkyl group; wherein the values of m,n, s and t independently lie in the range of from 0 to 8, the value of blies in the range from 0 to 20, and the values of a, u and vindependently are either 0 or 1 with the proviso that at least one of uor v must be 1; and wherein M is a counter anion.

Preferably R₂,R₃ and R₄ are independently selected from CH₃ and—CH₂CH₂OH. Preferably M is selected from the group consisting of halide,methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate,chloride, bromide or iodide. Preferred water dispersible cationic estersurfactants are the choline esters having the formula:

wherein R₁ is a C₁₁-C₁₉ linear or branched alkyl chain.

Particularly preferred choline esters of this type include the stearoylcholine ester quaternary methylammonium halides (R¹=C₁₇ alkyl),palmitoyl choline ester quaternary methylammonium halides (R¹=C₁₅alkyl), myristoyl choline ester quaternary methylammonium halides(R¹=C₁₃ alkyl), lauroyl choline ester methylammonium halides (R¹=C₁₁alkyl), cocoyl choline ester quaternary methylammonium halides(R¹=C₁₁-C₁₃ alkyl), tallowyl choline ester quaternary methylammoniumhalides (R¹=C₁₅-C₁₇ alkyl), and any mixtures thereof. The particularlypreferred choline esters, given above, may be prepared by the directesterification of a fatty acid of the desired chain length withdimethylaminoethanol, in the presence of an acid catalyst. The reactionproduct is then quaternized with a methyl halide, preferably in thepresence of a solvent such as ethanol, propylene glycol or preferably afatty alcohol ethoxylate such as C₁₀-C₁₈ fatty alcohol ethoxylate havinga degree of ethoxylation of from 3 to 50 ethoxy groups per mole formingthe desired cationic material. They may also be prepared by the directesterification of a long chain fatty acid of the desired chain lengthtogether with 2-haloethanol, in the presence of an acid catalystmaterial. The reaction product is then quaternized with trimethylamine,forming the desired cationic material.

Other suitable cationic ester surfactants have the structural formulasbelow, wherein d may be from 0 to 20.

Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formulaR³(OR⁴)_(x)N⁰(R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl,acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containingfrom 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene groupcontaining from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to5, preferably from 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl groupcontaining from 1 to 3, or a polyethylene oxide group containing from 1to 3 ethylene oxide groups. Preferred are C₁₀-C₁₈ alkyl dimethylamineoxide, and C₁₀₋₁₈ acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2MConc. manufactured by Miranol, Inc., Dayton, N.J.

Zwitterionic Surfactant

Zwitterionic surfactants can also be comprised in the surface activecomponent of the composition of the invention or the compositionscontaining the particle of the invention. These surfactants can bebroadly described as derivatives of secondary and tertiary amines,derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Betaine and sultaine surfactants are exemplaryzwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R′)₂N⁺R²COO⁻wherein R is a C₆-C₁₈ hydrocarbyl group, each R¹ is typically C₁-C₃alkyl, and R² is a C₁-C₅ hydrocarbyl group. Preferred betaines areC₁₂₋₁₈ dimethyl-ammonio hexanoate and the C₁₀₋₁₈ acylamidopropane (orethane) dimethyl (or diethyl) betaines. Complex betaine surfactants arealso suitable for use herein.

Alkali Metal Salt of Silicate

The granular compositions herein may comprise an alkali metal salt ofsilicate, or mixtures thereof, amongst the preferred optionalingredients. Preferred alkali metal salt of silicate to be used hereinis sodium silicate. In the preferred embodiment herein wherein thegranular compositions comprise an oxygen bleach and is typicallyintended for soaking application, it has been found that thedecomposition of available oxygen produced in the soaking liquors upondissolution of the granular compositions is reduced by the presence ofat least 40 parts per million of sodium silicate in said soakingliquors.

Any type of alkali metal salt of silicate can be used herein, includingthe crystalline forms as well as the amorphous forms of said alkalimetal salt of silicate or mixtures thereof.

Suitable crystalline forms of sodium silicate to be used are thecrystalline layered silicates of the granular formula

NaMSi_(x)O_(2x+1) .yH₂O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is anumber from 0 to 20, or mixtures thereof. Crystalline layered sodiumsilicates of this type are disclosed in EP-A-164 514 and methods fortheir preparation are disclosed in DE-A-34 17 649 and DE-A-37 42 043.For the purposes of the present invention, x in the general formulaabove has a value of 2, 3 or 4 and is preferably 2. More preferably M issodium and y is 0 and preferred examples of this formula comprise the a,b, g and d forms of Na₂Si₂O₅. These materials are available from HoechstAG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The mostpreferred material is d-Na₂Si₂O₅, NaSKS-6. Crystalline layered silicatesare incorporated in soaking compositions herein, either as dry mixedsolids, or as solid components of agglomerates with other components.

Suitable amorphous forms of sodium silicate to be used herein have thefollowing general formula:

NaMSi_(x)O_(2x+1)

wherein M is sodium or hydrogen and x is a number from 1.9 to 4, ormixtures thereof. Preferred to be used herein are the amorphous forms ofSi₂O₅Na₂O.

Suitable Zeolites for use herein are aluminosilicates including thosehaving the empirical formula:

Mz(zAlO2.ySiO2)

wherein M is sodium, potassium, ammonium or substituted ammonium, z isfrom about 0.5 to about 2; and y is 1; this material having a magnesiumion exchange capacity of at least about 50 milligram equivalents ofCaCO3 hardness per gram of anhydrous aluminosilicate. Preferred zeoliteswhich have the formula:

Nazí(AlO2)z(SiO2)yù.xH2O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful materials are commercially available. These aluminosilicates canbe crystalline or amorphous in structure and can be naturally-occurringaluminosilicates or synthetically derived. A method for producingaluminosilicate ion exchange materials is disclosed in U.S. Pat. No.3,985,669, Krummel, et al, issued Oct. 12, 1976. Preferred syntheticcrystalline aluminosilicate ion exchange materials useful herein areavailable under the designations Zeolite A, Zeolite P (B), and ZeoliteX. In an especially preferred embodiment, the crystallinealuminosilicate ion exchange material has the formula:

Na12í(AlO2)12(SiO2)12ù.xH2O

wherein x is from 20 to 30, especially about 27. This material is knownas Zeolite A. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Typically, the compositions herein may comprise from 0.5% to 15% byweight of the total composition of an alkali metal salt of silicate ormixtures thereof, preferably from 1 % to 10% and more preferably from 2%to 7%.

Builders

The granular compositions herein may also comprise a builder or amixture thereof. All builders known to those skilled in the art may beused herein. Suitable phosphate builders for use herein include sodiumand potassium tripolyphosphate, pyrophosphate, polymeric metaphosphatehaving a degree of polymerization of from about 6 to 21, andorthophosphate. Other phosphorus builder compounds are disclosed in U.S.Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and3,400,148, incorporated herein by reference.

Suitable polycarboxylate builders for use herein include etherpolycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S.Pat. No. 3,128,287, issued Apr. 7, 1964, and Lamberti et al, U.S. Pat.No. 3,635,830, issued Jan. 18, 1972. See also “TMS/TDS” builders of U.S.Pat. No. 4,663,071, issued to Bush et al, on May 5, 1987. Suitable etherpolycarboxylates also include cyclic compounds, particularly alicycliccompounds, such as those described in U.S. Pat. Nos. 3,923,679;3,835,163; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, 1,3,5-trihydroxy benzene-2,4,6-trisulphonicacid, and carboxymethyloxysuccinic acid, the various alkali metal,ammonium and substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Also suitable in the granular compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅-C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylate builders are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Other suitable polycarboxylate builders for use herein include buildersaccording to formula I

wherein Y is a comonomer or comonomer mixture; R¹ and R² are bleach- andalkali-stable polymer-end groups; R³ is H, OH or C₁₋₄ alkyl; M is H,alkali metal, alkaline earth metal, ammonium or substituted ammonium; pis from 0 to 2; and n is at least 10, or mixtures thereof.

Preferred polymers for use herein fall into two categories. The firstcategory belongs to the class of copolymeric polymers which are formedfrom an unsaturated polycarboxylic acid such as maleic acid, citraconicacid, itaconic acid, mesaconic acid and salts thereof as first monomer,and an unsaturated monocarboxylic acid such as acrylic acid or analpha-C₁₋₄ alkyl acrylic acid as second monomer. Referring to formula Ihereinabove, the polymers belonging to said first class are those wherep is not 0 and Y is selected from the acids listed hereinabove.Preferred polymers of this class are those according to formula Ihereinabove, where Y is maleic acid. Also, in a preferred embodiment, R³and M are H, and n is such that the polymers have a molecular weight offrom 1000 to 400 000 atomic mass units.

The second category of preferred polymers for use herein belongs to theclass of polymers in which, referring to formula I hereinabove, p is 0and R³ is H or C₁₋₄ alkyl. In a preferred embodiment n is such that thepolymers have a molecular weight of from 1000 to 400 000 atomic massunits. In a highly preferred embodiment, R³ and M are H.

The alkali-stable polymer end groups R¹ and R² in formula I hereinabovesuitably include alkyl groups, oxyalkyl groups and alkyl carboxylic acidgroups and salts and esters thereof

In the above, n, the degree of polymerization of the polymer can bedetermined from the weight average polymer molecular weight by dividingthe latter by the average monomer molecular weight. Thus, for amaleic-acrylic copolymer having a weight average molecular weight of15,500 and comprising 30 mole % of maleic acid derived units, n is 182(i.e. 15,500/(116×0.3+72×0.7)).

Temperature-controlled columns at 40° C. against sodium polystyrenesulphonate polymer standards, available from Polymer Laboratories Ltd.,Shropshire, UK, the polymer standards being 0.15M sodium dihydrogenphosphate and 0.02M tetramethyl ammonium hydroxide at pH 7.0 in 80/20water/acetonitrile.

Of all the above, highly preferred polymers for use herein are those ofthe first category in which n averages from 100 to 800, preferably from120 to 400.

Preferred builders for use herein are polymers of maleic or acrylicacid, or copolymers of maleic and acrylic acid.

Typically, the granular compositions of the present invention compriseup to 50% by weight of the total composition of a builder or mixturesthereof, preferably from 0.1 % to 20% and more preferably from 0.5 to11%.

Chelating Agents

Preferably the granular compositions herein further comprise a chelatingagent or mixtures thereof. Chelating agents are desired herein as theyhelp to control the level of free heavy metal ions in thewashing/soaking liquors, thus avoiding rapid decomposition of the oxygenreleased by oxygen bleach. Suitable amino carboxylate chelating agentswhich may be used herein include diethylene triamino pentacetic acid,ethylenediamine tetraacetates (EDTA), N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraamine hexaacetates, and ethanoldiglycines, alkali metalammonium and substituted ammonium salts thereof or mixtures thereof.Further suitable chelating agents includeethylenediamine-N,N′-disuccinic acids (EDDS) or alkali metal, alkalineearth metal, ammonium, or substituted ammonium salts thereof.Particularly suitable EDDS compounds are the free acid form and thesodium or magnesium salt or complex thereof. Also others suitablechelating agents may be the organic phosphonates, including aminoalkylene poly(alkylene phosphonate), alkali metal ethane 1-hydroxydiphosphonates, nitrilo trimethylene phosphonates, ethylene diaminetetra methylene phosphonates and diethylene triamine penta methylenephosphonates. The phosphonate compounds may be present either in theiracid form or in the form of their metal alkali salt. Preferably, theorganic phosphonate compounds where present are in the form of theirmagnesium salt.

The granular compositions in the present invention may accordinglycomprise from 0% to 5% by weight of the total compositions of saidchelating agents, preferably from 0% to 3%, more preferably from 0.05%to 2%.

Fillers

The granular compositions herein may further comprise a filler likeinorganic filler salts such as sulphates. Typically, the compositions ofthe present invention comprise up to 50% by weight of the totalcomposition of a filler or a mixture thereof, preferably from 0.1% to20% and more preferably from 0.5 % to 10%.

Enzymes

The granular compositions herein typically also comprise an enzyme or amixture thereof. Preferably the compositions herein comprise a proteaseor mixtures thereof. Protease enzymes are usually present in preferredembodiments of the invention at levels sufficient to provide from 0.005to 0.2 Anson units (AU) of activity per gram of composition. Theproteolytic enzyme can be of animal, vegetable or, preferablymicroorganism preferred origin. More preferred is serine proteolyticenzyme of bacterial origin. Purified or nonpurified forms of enzyme maybe used. Proteolytic enzymes produced by chemically or geneticallymodified mutants are included by definition, as are close structuralenzyme variants. Particularly preferred by way of proteolytic enzyme isbacterial serine proteolytic enzyme obtained from Bacillus, Bacillussubtilis and/or Bacillus licheniformis. Suitable commercial proteolyticenzymes include Alcalase®, Esperase®, Durazym®, Savinase®, Maxatase®,Maxacal®, and Maxapem® 15 (protein engineered Maxacal); Purafect® andsubtilisin BPN and BPN′ are also commercially available. Preferredproteolytic enzymes also encompass modified bacterial serine proteases,such as those described in European Patent Application Serial Number87303761.8, filed Apr. 28, 1987 (particularly pages 17, 24 and 98), andwhich is called herein “Protease B”, and in European Patent Application199,404, Venegas, published Oct. 29, 1986, which refers to a modifiedbacterial serine proteolytic enzyme, which is called “Protease A”herein. More preferred is what is called herein “Protease C”, which is atriple variant of an alkaline serine protease from Bacillus in whichtyrosine replaced valine at position 104, serine replaced asparagine atposition 123, and alanine replaced threonine at position 274. Protease Cis described in EP 90915958.4, corresponding to WO 91/06637, PublishedMay 16, 1991, which is incorporated herein by reference. Geneticallymodified variants, particularly of Protease C, are also included herein.

Also suitable for use herein is a protease herein referred to as“Protease D” which is a carbonyl hydrolase variant having an amino acidsequence not found in nature, which is derived from a percursor carbonylhydrolase by substituting a different amino acid for a plurality ofamino acid residues at a position in said carbonyl hydrolase equivalentto position +76 in combination with one or more amino acid residuepositions equivalent to those selected from the group consisting of +99,+101, +103, +107 and +123 in Bacillus amyloliguefaciens subtilisin asdescribed in the concurrently filed patent applications of A. Baeck, C.K. Ghosh, P. P. Greycar, R. R. Bott and L. J. Wilson, entitled“Protease-Containing Cleaning Compositions” having U.S. Ser. No.08/136,797 (P&G Case 5040), now abandoned, and “Bleaching CompositionsComprising Protease Enzymes” having U.S. Ser. No. 08/136,626, nowabandoned, which are incorporated herein by reference.

Some preferred proteolytic enzymes are selected from the groupconsisting of Savinase®, Esperase®, Maxacal®, Purafect®, BPN′, ProteaseA and Protease B, and mixtures thereof. Bacterial serine proteaseenzymes obtained from Bacillus subtilis and/or Bacillus licheniformisare preferred. Particularly preferred are Savinase®, Alcalase®, ProteaseA and Protease B.

Typically, the granular compositions herein also comprise an amylase ora mixtures thereof Engineering of enzymes for improved stability, e.g.oxidative stability is known. See, for example J. Biological Chem., vol.260, No. 11, June 1985, pp 6518-6521. “Reference amylase” hereinafterrefers to an amylase outside the scope of the amylase component of thisinvention and against which stability of any amylase within theinvention can be measured.

The present invention thus makes use of amylases having improvedstability in detergents, especially improved oxidative stability. Aconvenient absolute stability reference-point against which amylasesused in the instant invention represent a measurable improvement is thestability of TERMAMYL (R) in commercial use in 1993 and available fromNovo Nordisk A/S. This TERMAMYL (R) amylase is a “reference amylase”.Amylases within the spirit and scope of the present invention share thecharacteristic of being “stability-enhanced” amylases, characterised, ata minimum, by a measurable improvement in one or more of: oxidativestability, e.g. to hydrogen peroxide/tetraacetylethylenediamine inbuffered solution at pH 9-10; thermal stability, e.g. at common washtemperatures such as about 60° C; or alkaline stability, e.g. at a pHfrom about 8 to about 11, all measured versus the above-identifiedreference-amylase. Preferred amylases herein can demonstrate furtherimprovement versus more challenging reference amylases, the latterreference amylases being illustrated by any of the precursor amylases ofwhich the amylases within the invention are variants. Such precursoramylases may themselves be natural or be the product of geneticengineering. Stability can be measured using any of the art-disclosedtechnical tests. See references disclosed in WO 94/02597, itself anddocuments therein referred to being incorporated by reference.

In general, stability-enhanced amylases respecting the invention can beobtained from Novo Nordisk A/S, or from Genencor International.

Preferred amylases herein have the common ability of being derived usingsite-directed mutagenesis from one or more of the Bacillus amylases,especially the Bacillus alpha-amylases, regardless of whether one, twoor multiple amylase strains are the immediate precursors.

As noted, “oxidative stability-enhanced” amylases are preferred for useherein. Such amylases are non-limitingly illustrated by the following:

(a) An amylase according to the hereinbefore incorporated WO/94/02597,Novo Nordisk A/S, published Feb. 3, 1994, as further illustrated by amutant in which substitution is made, using alanine or threonine(preferably threonine), of the methionine residue located in position197 of the Bacillus licheniformis alpha-amylase, known as TERMAMYL (R),or the homologous position variation of a similar parent amylase, suchas Bacillus amyloliquefaciens, Bacillus subtilis, or Bacillusstearothermophilus;

(b) Stability-enhanced amylases as described by Genencor Internationalin a paper entitled “Oxidatively Resistant alpha-Amylases” presented atthe 207th American Chemical Society National Meeting, Mar. 13-17, 1994,by C. Mitchinson. Therein it was noted that bleaches in automaticdishwashing detergents inactivate alpha-amylases but that improvedoxidative stability amylases have been made by Genencor from Bacilluslicheniformis NCIB8061. Methionine (Met) was identified as the mostlikely residue to be modified. Met was substituted, one at a time, inpositions 8,15,197,256,304,366 and 438 leading to specific mutants,particularly important being M197L and M197T with the M197T variantbeing the most stable expressed variant. Stability was measured inCASCADE (R) and SUNLIGHT (R); Such enzymes are commercially availablefrom Genencor under the trade name Plurafact Oxam®.

(c) Particularly preferred herein are amylase variants having additionalmodification in the immediate parent available from Novo Nordisk A/S.These amylases do not yet have a tradename but are those referred to bythe supplier as QL37+M197T. Such enzymes are commercially availableunder the trade name SP 703 from Novo.

Any other oxidative stability-enhanced amylase can be used, for exampleas derived by site-directed mutagenesis from known chimeric, hybrid orsimple mutant parent forms of available amylases.

Soil Suspending Agents

The granular compositions herein may also comprise a soil suspendingagent or a mixture thereof, typically at a level up to 20% by weight,preferably from 0.1% to 10%, more preferably from 0.5% to 2%. Suitablesoil suspending agents include ethoxylated diamines, ethoxylatedpolyamines, ethoxylated amine polymers as described in EP-A-112 593,incorporated herein by reference. Preferred soil suspending agents to beused herein include ethoxylated polyethyleneamine having a molecularweight of from 140 to 310 prior ethoxylation, ethoxylated 15-18tetraethylenepentamine, ethoxylated 15-18 polyethylenamine, ethoxylated15-18 ethylenediamine, ethoxylated polyethyleneimine having a molecularweight of from 600 to 1800 prior ethoxylation, and mixtures thereof.

Suds Suppressing Systems

The detergent compositions of the invention, when formulated for use inmachine washing compositions, preferably comprise a suds suppressingsystem present at a level of from 0.01% to 15%, preferably from 0.05% to10%, most preferably from 0.1% to 5% by weight of the composition.

Suitable suds suppressing systems for use herein may compriseessentially any known antifoam compound, including, for example siliconeantifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures ofcompounds which act such as to depress the foaming or sudsing producedby a solution of a detergent composition, particularly in the presenceof agitation of that solution.

Particularly preferred antifoam compounds for use herein are siliconeantifoam compounds defined herein as any antifoam compound including asilicone component. Such silicone antifoam compounds also typicallycontain a silica component. The term “silicone” as used herein, and ingeneral throughout the industry, encompasses a variety of relativelyhigh molecular weight polymers containing siloxane units and hydrocarbylgroup of various types. Preferred silicone antifoam compounds are thesiloxanes, particularly the polydimethylsiloxanes having trimethylsilylend blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acidsand soluble salts thereof. These materials are described in U.S. Pat.No. Pat. No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. Themonocarboxylic fatty acids, and salts thereof, for use as sudssuppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,preferably 12 to 18 carbon atoms. Suitable salts include the alkalimetal salts such as sodium, potassium, and lithium salts, and ammoniumand alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecularweight fatty esters (e.g. fatty acid triglycerides), fatty acid estersof monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g. stearone)N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, bis stearic acid amideand monostearyl di-alkali metal (e.g. sodium, potassium, lithium)phosphates and phosphate esters.

A preferred suds suppressing system comprises

(a) antifoam compound, preferably silicone antifoam compound, mostpreferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75%to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% byweight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incorporated at alevel of from 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycolrake copolymer with a polyoxyalkylene content of 72-78% and an ethyleneoxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level offrom 0.5% to 10%, preferably 1% to 10% by weight; a particularlypreferred silicone glycol rake copolymer of this type is DC0544,commercially available from DOW Corning under the tradename DC0544;

(c) an inert carrier fluid compound, most preferably comprising aC₁₆-C₁₈ ethoxylated alcohol with a degree of ethoxylation of from 5 to50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to70%, by weight;

A highly preferred particulate suds suppressing system is described inEP-A-0210731 and comprises a silicone antifoam compound and an organiccarrier material having a melting point in the range 50° C. to 85° C.,wherein the organic carrier material comprises a monoester of glyceroland a fatty acid having a carbon chain containing from 12 to 20 carbonatoms. EP-A-0210721 discloses other preferred particulate sudssuppressing systems wherein the organic carrier material is a fatty acidor alcohol having a carbon chain containing from 12 to 20 carbon atoms,or a mixture thereof, with a melting point of from 45° C. to 80° C.

Clay Softening Systems

The detergent compositions of the present invention typically intendedfor washing fabrics in domestic washing machine may contain a claysoftening system comprising a clay mineral compound and optionally aclay flocculating agent.

The clay mineral compound is preferably a smectite clay compound.Smectite clays are disclosed in the U.S. Pat. No. Pat. Nos. 3,862,058,3,948,790, 3,954,632 and 4,062,647. European Patents Nos. EP-A-299,575and EP-A-313,146 in the name of the Procter and Gamble Company describesuitable organic polymeric clay flocculating agents.

Polymeric Dye Transfer Inhibiting Agents

The detergent compositions of the present invention typically intendedfor washing fabrics in domestic washing machine may also comprise from0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dyetransfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selectedfrom polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

a) Polyamine N-oxide Polymers

Polyamine N-oxide polymers suitable for use herein contain units havingthe following structure formula:

wherein P is a polymerisable unit, and

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic oralicyclic groups or any combination thereof whereto the nitrogen of theN—O group can be attached or wherein the nitrogen of the N—O group ispart of these groups.

The N—O group can be represented by the following general structures:

wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic oralicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1and wherein the nitrogen of the N—O group can be attached or wherein thenitrogen of the N—O group forms part of these groups. The N—O group canbe part of the polymerisable unit (P) or can be attached to thepolymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N—O group forms part of thepolymerisable unit comprise polyamine N-oxides wherein R is selectedfrom aliphatic, aromatic, alicyclic or heterocyclic groups. One class ofsaid polyamine N-oxides comprises the group of polyamine N-oxideswherein the nitrogen of the N—O group forms part of the R-group.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine,quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto theN—O group is attached to the polymerisable unit. A preferred class ofthese polyamine N-oxides comprises the polyamine N-oxides having thegeneral formula (I) wherein R is an aromatic,heterocyclic or alicyclicgroups wherein the nitrogen of the N—O functional group is part of saidR group. Examples of these classes are polyamine oxides wherein R is aheterocyclic compound such as pyrridine, pyrrole, imidazole andderivatives thereof.

The polyamine N-oxides can be obtained in almost any degree ofpolymerisation. The degree of polymerisation is not critical providedthe material has the desired water-solubility and dye-suspending power.Typically, the average molecular weight is within the range of 500 to1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are copolymers of N-vinylimidazole andN-vinylpyrrolidone having an average molecular weight range of from5,000 to 50,000. The preferred copolymers have a molar ratio ofN-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone(“PVP”) having an average molecular weight of from 2,500 to 400,000.Suitable polyvinylpyrrolidones are commercially available from ISPCorporation, New York, N.Y. and Montreal, Canada under the product namesPVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (averagemolecular weight of 40,000), PVP K-60 (average molecular weight of160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15is also available from ISP Corporation. Other suitablepolyvinylpyrrolidones which are commercially available from BASFCooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions herein may also utilize polyvinyloxazolidonesas polymeric dye transfer inhibiting agents. Said polyvinyloxazolidoneshave an average molecular weight of from 2,500 to 400,000.

e) Polyvinylimidazole

The detergent compositions herein may also utilize polyvinylimidazole aspolymeric dye transfer inhibiting agent. Said polyvinylimidazolespreferably have an average molecular weight of from 2,500 to 400,000.

Optical Brighteners

The detergent compositions herein also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners.

Hydrophilic optical brighteners useful herein include those having thestructural formula:

wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium. When in the aboveformula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl and M is a cationsuch as sodium, the brightener is4,4′-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein. When in theabove formula, R₁ is anilino, R₂ is N-2-hydroxyethyl-N-2-methylamino andM is a cation such as sodium, the brightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Cationic Fabric Softening Agents

Cationic fabric softening agents can also be incorporated into thegranular compositions of the present invention. Suitable cationic fabricsoftening agents include the water insoluble tertiary amines or dilongchain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.Cationic fabric softening agents are typically incorporated at totallevels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.

The Process of Soaking Fabrics

The present invention encompasses processes of soaking fabrics. Indeed,the present invention encompasses a process of soaking fabrics, whereinsaid fabrics are immersed in a soaking liquor comprising water and aneffective amount of a granular composition as described hereinbefore,for an effective period of time, then removed from said soaking liquor.

As used herein, the expression “process of soaking fabrics” refers tothe action of leaving fabrics to soak in a soaking liquor comprisingwater and a composition as described hereinabove, for a period of timesufficient to clean said fabrics. In contrast to typical launderingoperation using a washing machine, the soaking process herein allowsprolonged contact time between the fabrics and the soaking liquor,typically up to 24 hours. The soaking process can be performedindependently from any other process, such as a typical launderingoperation, or a first step before a second typical laundering step, or asecond step after a first typical laundering operation. In the preferredsoaking processes of the invention, fabrics are left to soak for aperiod of time ranging from 1 minute to 24 hours, preferably from 10minutes to 24 hours, more preferably from 30 minutes to 18 hours, evenmore preferably 1 hour to 6 hours. After the fabrics have been immersedin said soaking liquor for a sufficient period of time, they can beremoved and rinsed with water. The fabrics can also be washed in anormal laundering operation after they have been soaked, with or withouthaving been rinsed in-between the soaking operation and the subsequentlaundering operation.

In the soaking process herein, a soaking composition describedhereinabove is diluted in an appropriate amount of water to produce asoaking liquor. Suitable doses may range from 40 to 55 grams of soakingcomposition in 3.5 to 5 liters of water, down to 90 to 100 grams ofsoaking composition in 20 to 45 liters of water. Typically one dose is40-55 grams in 3.5 to 5 liters for a concentrated soak (bucket/sink).For washing machine soaked, the dose is 90-100 grams in about 20(Europe) to 45 (U.S.) liters of water. The fabrics to be soaked are thenimmersed in the soaking liquor for an appropriate period of time. Thereare factors which may influence overall stain removal performance of theprocess on various dirt/soils. Such factors include prolonged soakingtime. Indeed, the longer fabrics are soaked, the better the end results.Thus the instructions on commercially available soaking compositionsideally recommend overnight soaking time, i.e., 8 hours up to 24 hours.An advantage of the present invention is that effective results areobtained even in short soaking operations, typically below 30 minutes.Another factor is the initial warm or warmluke temperature. Indeed,higher initial temperatures of the soaking liquors ensure large benefitsin performance. Another advantage of the present invention is thateffective results are obtained even at low soaking temperature,typically below 30° C., or even below 20° C.

The process herein is suitable for cleaning a variety of fabrics, butfinds a preferred application in the soaking of socks, which areparticularly exposed to silt and clay pick-up.

The Process of Washing Fabrics in Laundry Domestic Washing Machine

The present invention encompasses processes of washing fabrics. Indeed,the present invention encompasses a process of washing fabrics in adomestic washing machine comprising, introducing into a dispensingdevice which is placed in the drum of the washing machine, orintroducing into the dispensing drawer of a washing machine, aneffective amount of a granular detergent composition comprising a dryeffervescent granules as described herein.

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is meant from 40 g to 300 g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65liters, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

In a preferred use aspect a dispensing device is employed in the washingmethod. The dispensing device is charged with the detergent product, andis used to introduce the product directly into the drum of the washingmachine before the commencement of the wash cycle. Its volume capacityshould be such as to be able to contain sufficient detergent product aswould normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensingdevice containing the detergent product is placed inside the drum. Atthe commencement of the wash cycle of the washing machine water isintroduced into the drum and the drum periodically rotates. The designof the dispensing device should be such that it permits containment ofthe dry detergent product but then allows release of this product duringthe wash cycle in response to its agitation as the drum rotates and alsoas a result of its contact with the wash water.

To allow for release of the detergent composition during the wash thedevice may possess a number of openings through which the product maypass. Alternatively, the device may be made of a material which ispermeable to liquid but impermeable to the solid product, which willallow release of dissolved product. Preferably, the detergent productwill be rapidly released at the start of the wash cycle therebyproviding transient localised high concentrations of product in the drumof the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a waythat container integrity is maintained in both the dry state and duringthe wash cycle. Especially preferred dispensing devices for use with thecomposition of the invention have been described in the followingpatents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345and EP-A-0288346. An article by J.Bland published in ManufacturingChemist, November 1989, pages 41-46 also describes especially preferreddispensing devices for use with granular laundry products which are of atype commonly know as the “granulette”. Another preferred dispensingdevice for use with the compositions of this invention is disclosed inPCT Patent Application No. WO94/11562. Especially preferred dispensingdevices are disclosed in European Patent Application Publication Nos.0343069 & 0343070. The latter Application discloses a device comprisinga flexible sheath in the form of a bag extending from a support ringdefining an orifice, the orifice being adapted to admit to the bagsufficient product for one washing cycle in a washing process. A portionof the washing medium flows through the orifice into the bag, dissolvesthe product, and the solution then passes outwardly through the orificeinto the washing medium. The support ring is provided with a maskingarrangement to prevent egress of wetted, undissolved, product, thisarrangement typically comprising radially extending walls extending froma central boss in a spoked wheel configuration, or a similar structurein which the walls have a helical form. Alternatively, the dispensingdevice may be a flexible container, such as a bag or pouch. The bag maybe of fibrous construction coated with a water impermeable protectivematerial so as to retain the contents, such as is disclosed in Europeanpublished Patent Application No. 0018678. Alternatively it may be formedof a water-insoluble synthetic polymeric material provided with an edgeseal or closure designed to rupture in aqueous media as disclosed inEuropean published Patent Application Nos. 0011500, 0011501, 0011502,and 0011968. A convenient form of water frangible closure comprises awater soluble adhesive disposed along and sealing one edge of a pouchformed of a water impermeable polymeric film such as polyethylene orpolypropylene.

Packaging for the Granular Compositions

Commercially marketed executions of the granular compositions can bepackaged in any suitable container including those constructed frompaper, cardboard, plastic materials and any suitable laminates.

Form of the Cleaning Compositions

The granular compositions can be made via a variety of methods,including dry-mixing, extruding, compressing and agglomerating of thevarious components comprised in the detergent composition. The dryeffervescence granule of the invention can be present in the cleaningcompositions as a separate component of the composition, or can be partof or added to other components or compounds of the compositions.

The cleaning compositions can take a variety of physical forms includinggranular, flakes, extrudates, tablet or bar forms. The cleaningcompositions are particularly the so-called concentrated granulardetergent compositions adapted to be added to a washing machine by meansof a dispensing drawer or by means of a dispensing device placed in themachine drum with the soiled fabric load.

The mean particle size of the base composition of granular cleaningcompositions containing the foaming composition in accordance with theinvention can be from 0.1 mm to 5.0 mm, but it should preferably be suchthat no more that 5% of particles are greater than 2.5 mm in diameter,or even 1.7 mm and that not more than 5% of particles are less than 0.15 mm in diameter.

The term mean particle size as defined herein is calculated by sieving asample of the composition into a number of fractions (typically 5fractions) on a series of Tyler sieves. The weight fractions therebyobtained are plotted against the aperture size of the sieves. The meanparticle size is taken to be the aperture size through which 50% byweight of the sample would pass.

The bulk density of granular cleaning or detergent compositionscontaining the particulate composition in accordance with the presentinvention typically have a bulk density of at least 300 g/liter, morepreferably from 500 g/liter or even 650 g/liter to 1200 g/liter, morepreferably to 850 g/liter.

The Stain Removal Performance Test Method

The stain removal performance of a given composition on a soiled fabricfor example under soaking conditions, may be evaluated by the followingtest method. Soaking liquors are formed by diluting for instance 45 g ofthe soaking compositions herein in 3.78 liter of water or 90 g of thesoaking composition in 45 liters of water. Fabrics are then immersed inthe resulting soaking liquor for a time ranging from 1 minute totypically 18 hours. Finally, the fabrics are removed from the soakingliquors, rinsed with water and washed with a regular washing process,handwash or washing machine wash, with a regular detergent, with orwithout re-using the soaking liquor, then said fabrics are left to dry.

For example, typical soiled fabrics to be used in this stain removalperformance test may be commercially available from EMC (EmpiricalManufacturing Company) Cincinnati, Ohio, USA, such as clay, grass,spaghetti sauce, gravy, dirty motor oil, barbecue sauce, blood on twodifferent substrates: cotton (CW120) and polycotton (PCW28).

The stain removal performance may be evaluated by comparing side by sidethe soiled fabrics treated with the composition according to the presentinvention with those treated with the reference, e.g., the samecomposition without such dry effervescent granules according to thepresent invention. A visual grading scale may be used to assigndifferences in panel score units (psu), in a range from 0 to 4.

The Thermal Stability Test Method

To evaluate thermal stability of a given composition, a sample thereofmay be placed in an oven whose temperature is setted at 60° C. When thesample reaches the oven temperature (60° C.), it is isolated with anadiabatic bell and its temperature is monitored for 2 hours. The selfheating rate is determined (SHR, average temperature increase over thefirst 2 hours).. The lower the SHR the more stable is the composition.

the Effervescence Test Method

Effervescence of a given granular composition may be measured via visualgrading. A composition according to the present invention and areference composition without the dry effervescent granules, or areference composition wherein the effervescent materials are uniformlyand separately distributed in the whole granular composition, are eachindividually diluted into 5 liters of water at 35° C. and the resultinggeneration of carbon dioxide is evaluated by visual grading.

The Dissolution Test Method

Dissolution characteristics of a given granular composition ma y bemeasured via visual grading. A composition according to the presentinvention and a reference composition without the dry effervescentgranules, or a reference composition wherein the effervescent materialsare uniformly and separately distributed in the whole granularcomposition, are each individually diluted into 2 liters of water at 5°C. Then the water is evaporated with a standard evaporator with a blackfabric instead of a paper filter. A visual grading scale may be used toassign differences in panel score units (psu), in a range from 0 to 4.

The Dispensing Test Method

Dispensing can be evaluated by means of a standard test using a washingmachine by introducing a given weight of composition in the dispenserand flowing water over a given period of time. Then measuring the dryweight of laundry detergent composition remaining in the dispenser, ingrams, and calculating the weight percentage of composition notdispensed into the machine.

Bulk Density Test Method

Bulk density of the granular composition and/or of the dry effervescentgranules of the present invention may be measured by means of a simplefunnel and cup device consisting of a conical funnel moulded rigidly ona base and provided with a flap valve at its lower extremity to allowthe contents of the funnel to be emptied into an axially alignedcylindrical cup disposed below the funnel. The funnel is 130 mm high andhas internal diameters of 130 mm and 40 mm at its respective upper andlower extremities. It is mounted so that the lower extremity is 140 mmabove the upper surface of the base. The cup has an overall height of 90mm, an internal height of 87 mm and an internal diameter of 84 mm. Itsnominal volume is 500 ml. To carry out a measurement, the funnel isfilled with powder by hand pouring, the flap valve is opened and powderallowed to overfill the cup. The filled cup is removed from the frameand excess powder removed from the cup by passing a straight edgedimplement e.g.; a knife, across its upper edge. The filled cup is thenweighed and the value obtained for the weight of powder doubled toprovide a bulk density in g/liter. Replicate measurements are made asrequired.

The following examples will further illustrate the present invention.

EXAMPLES

I) Soaking Compositions

The following soaking compositions are prepared by mixing the listedingredients in the listed proportions.

Ingredients (% w/w) (% w/w) (% w/w) 1 2 3 Sodium percarbonate 22 22 22Alcohol ethoxylated EO 25 2 — — Alcohol ethoxylated EO 11 — 2 — Alcoholethoxylated EO 50 — — 2 Anionic (LAS/AS/AES) 8 8 8 DTPA 0.2 0.2 0.2 TAED8.3 5 5 Dry Effervescent granule 20 10 10 sodium bicarbonate 40% sodiumcarbonate 16% Malic acid 44% Minors and inerts up to 100 up to 100 up to100 4 5 6 Sorbitan mono-stearate (SMS) 2.5 — — Sorbitan monostearate EO20 — 3.0 — (SMS EO 20) Sorbitan tristearate EO 20 0.5 — 3.0 (STS EO 20)Citric acid 10 10 10 Polyacrylate (Acusol 445 ND ®) 11 11 11 Silicate(amorphous; 1.6 r) 0.4 0.4 0.4 Sodium percarbonate 31 31 31 NOBS 6 6 6TAED 5 5 5 Anionic (LAS/AS/AES) 7 7 7 Alcohol EO 25 2 2 2 DryEffervescent granule 20 20 20 sodium bicarbonate 40% sodium carbonate16% malic acid 40% citric acid 4% Others, inerts and minors up to 100 upto 100 up to 100 7 8 9 Sodium percarbonate 22 22 22 Alcohol ethoxylatedEO 25 2 2 2 Anionic (LAS/AS/AES/NaPS) 10 10 10 Enzymes (amylase, lipase,protease) 1.9 1.9 1.9 Zeolites 6.0 4.0 2.0 Polymers (polycarboxylate,carboxy 7.5 7.5 7.5 methilcellulose) DTPA 0.2 0.2 0.2 TAED 8.0 8.0 8.0NOBS 4.0 — — Brightener 0.15 0.15 0.15 Zn pthalocyanine sulphonate 0.060.06 0.06 Hydroxyethylidendiphosphonate 0.18 0.18 0.18 Dry Effervescentgranule 20 15 10 sodium bicarbonate 40% sodium carbonate 10% Malic acid44% LAS 6% Minors and inerts up to 100 up to 100 up to 100 10 11 12Sodium percarbonate 45 40 35 Anionic (LAS/AS/AES) 8 8 8 DTPA 0.2 0.2 0.2TAED 8.3 8.3 8.3 Brightener 0.15 0.15 0.15 Zn pthalocyanine sulphonate0.06 0.06 0.06 Enzymes (amylase, lipase, protease) 1.9 1.9 1.9 DryEffervescent granule 20 15 10 sodium bicarbonate 40% sodium carbonate16% Malic acid 44% Minors and inerts up to 100 up to 100 up to 100 TAEDis tetracetyl ethylene. NOBS is n-nonanoyloxybenzenesulphonate. NaPS issodium parraffin sulphonate. DTPA is Diethylene-triamine-Penta Aceticacid. LAS is C12 alkylbenzene sulphonate.

Soaking liquors are formed by diluting each time 45 g of the abovecompositions in between 3.5 lit. to 5.0 lit. of water. 0.5 to 2 Kg offabrics are then each time immersed in said soaking liquor. The soakingperiods for the soaking liquors comprising any of the soakingcompositions 1 to 12 are typically from 1 minute to 24 hours.

Finally, the fabrics are removed from the soaking liquors, rinsed withwater and washed with a regular washing process, handwash or washingmachine wash, with a regular detergent, with or without re-using thesoaking liquor, then said fabrics are left to dry. Excellent stainremoval performance is obtained with these compositions on variousstains including greasy stains and/or enzymatic stains and/or bleachablestains and the like.

Example of Process for Manufacturing the Dry Effervescent GranulesAccording to the Present Invention

The following process may be carried out to form a dry effervescentgranule consisting of 40% by weight of the total granule of bicarbonate,40% by weight of malic acid, 16% by weight of carbonate, and 4% byweight of citric acid. In a first step the respective ingredients aremixed together at the respective levels. Then the obtained mixture isincorporated in a Pharmapaktor L200/50P® commercially available fromHosokawa Bepex GmbH. The distance between the rolls is about 5 cm, thepressing force applied during the compaction step is about 60 kN, theroll speed is about 15 rpm and the feed screw is about 14 rpm. In thePharmapaktor L200/50P® the mixture is forced between the compactionrolls so as to form a compacted flake/sheet. This compacted sheet/flakeis then milled with a Flake Crusher FC 200® with a mesh size of 1.2 mm.A bar-head is installed on the Flake Crusher FC 200®. The processtemperature is at about 25° C. The resulting granules are thenincorporated in a granular composition according to the presentinvention (e.g. compositions 4 to 6 above).

II) Laundry Washing Machine Detergent Compositions

In the detergent compositions, the abbreviated component identificationshave the following meanings:

LAS Sodium linear C₁₂ alkyl benzene sulfonate TAS Sodium tallow alkylsulfate C45AS Sodium C₁₄-C₁₅ linear alkyl sulfate MES α-sulphomethylester of C₁₈ fatty acid CxyEzS Sodium C_(1x)-C_(1y) branched alkylsulfate condensed with z moles of ethylene oxide MBAS_(x,y) Sodiummid-chain branched alkyl sulfate having an average of x carbon atoms,whereof an average of y carbons comprised in (a) branching unit(s) C₄₈SAS Sodium C₁₄-C₁₈ secondary alcohol sulfate SADExS Sodium C₁₄-C₂₂ alkyldisulfate of formula 2-(R).C₄ H₇-1,4-(SO₄-)₂ where R = C₁₀0C₁₈,condensed with z moles of ethylene oxide CxyEz A C_(1x-1y) branchedprimary alcohol condensed with an average of z moles of ethylene oxideQAS I R₂.N⁺(CH₃)₂(C₂H₄OH) with R₂ = 50%-60% C₉; 40%-50% C₁₁ QAS IIR₁.N⁺(CH₃)(C₂H₄OH)₂ with R₁ = C₁₂-C₁₄ Soap Sodium linear alkylcarboxylate derived from an 80/20 mixture of tallow and coconut oils.TFAA I C₁₂-C₁₄ alkyl N-methyl glucamide TFAA II C₁₆-C₁₈ alkyl N-methylglucamide TPKFA C₁₂-C₁₄ topped whole cut fatty acids STPP Anhydroussodium tripolyphosphate Zeolite A I Hydrated Sodium Aluminosilicate offormula Na₁₂(A10₂SiO₂)₁₂.27H₂O having a primary particle size in therange from 0.1 to 10 micrometers Zeolite A II overdried Zeolite A INaSKS-6 Crystalline layered silicate of formula δ-Na₂Si₂O₅ Citric acid IAnhydrous citric acid Citric acid II Citric acid monohydrate Malic acidAnhydrous malic acid Maleic acid Anhydrous maleic acid Tartaric acidAnhydrous aspartic acid Carbonate I Anhydrous sodium carbonate with anaverage particle size between 200 μm and 900 μm Carbonate II Anhydroussodium carbonate with an average particle size between 100 μm and 200 μmBicarbonate Anhydrous sodium bicarbonate with a particle sizedistribution between 400 μm and 1200 μm Silicate Amorphous SodiumSilicate (SiO₂:Na₂O; 2.0 ratio) Sodium sulfate Anhydrous sodium sulfateCitrate Tri-sodium citrate dihydrate of activity 86.4% with a particlesize distribution between 425 μm and q 850 μm MA/AA Copolymer of 1:4maleic/acrylic acid, average molecular weight about 70,000 CMC Sodiumcarboxymethyl cellulose Protease Proteolytic enzyme of activity 4KNPU/gsold by NOVO Industries A/S under the tradename Savinase AlcalaseProteolytic enzyme of activity 3 AU/g sold by NOVO Industries A/SCellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVOIndustries A/S under the tradename Carezyme Amylase Amylolytic enzyme ofactivity 60KNU/g sold by NOVO Industries A/S under the tradenameTermamyl 60T Lipase Lipolytic enzyme of activity 100kU/g sold by NOVOIndustries A/S under the tradename Lipolase Endolase Endoglunase enzymeof activity 3000 CEVU/g sold by NOVO Industries A/S PB4 Sodium perboratetetrahydrate of nominal formula NaBO₂.3H₂O.H₂O₂ PB1 Anhydrous sodiumperborate bleach of nominal formula NaBO₂.H₂O₂ Percarbonate SodiumPercarbonate of nominal formula 2NaCO3.3H2O2 NAC-OBS (Nonanamidocaproyl) oxybenzene sulfonate in the form of the sodium salt. NOBSNonanoyl oxybenzene sulfonate in the form of the sodium salt DPDADiperoxydodecanedioic acid PAP N-phthaloylamidoperoxicaproic acid NAPAANonanoylamido peroxo-adipic acid NACA 6 nonylamino-6 oxo-caproic acid.TAED Tetraacetylethylenediamine DTPMP Diethylene triamine penta(methylene phosphonate), marketed by Monsanto under the Trade nameDequest 2060 Photoactivated Sulfonated Zinc or aluminium Phthlocyanineencapsulated Brightener 1 Disodium 4,4′-bis(2-sulphostyryl)biphenylBrightener 2 Disodium 4,4′-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino)stilbene-2:2′-disulfonate. HEDP 1,1-hydroxyethanediphosphonic acid PVNO Polyvinylpyridine N-oxide PVPVI Copolymer ofpolyvinylpyrolidone and vinylimidazole QEA bis((C₂H₅O)(C₂H₄O)_(n))(CH₃)-N⁺-C₆H₁₂-N⁺- (CH₃)bis((C₂H₅O)-(C₂H₄O)_(n)),wherein n = from 20 to 30 SRP 1 Sulfobenzoyl end capped esters withoxyethylene oxy and terephtaloyl backbone SRP 2 Diethoxylated poly(1,2propylene terephtalate) short block polymer SiliconePolydimethylsiloxane foam controller with siloxane- antifoam oxyalkylenecopolymer as dispersing agent with a ratio of said foam controller tosaid dispersing agent of 10:1 to 100:1.

In the following examples all levels are quoted as % by weight of thecomposition:

The following high density granular laundry detergent compositions A toF of particular utility under European machine wash conditions wereprepared in accord with the invention:

A B C D E F LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4C46AS 1.0 2.0 2.5 — 3.0 4.0 C68AS 3.0 2.0 5.0 7.0 1.0 0.5 QAS I — — 0.8— — 0.8 Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1 Zeolite MAP — 4.0 3.5 —— — Carbonate I 12.0 12.0 11.5 25.0 25.0 25.0 Silicate 1.4 1.4 1.4 3.03.0 3.0 MA/AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 PB49.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5 1.0 1.5 — 1.5 Mn Catalyst — 0.030.07 — — — DTPMP 0.25 0.25 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.2 0.2 0.30.3 EDDS — — 0.4 0.2 — — QEA 1 1.0 0.8 0.7 1.2 — 0.5 Protease 0.26 0.260.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.4 0.3 0.1 0.1 Lipase 0.05 0.6 0.70.1 0.07 0.1 Photoactivated bleach 15 15 15 15 15 15 (ppm) ppm ppm ppmppm ppm ppm Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09 Perfume 0.3 0.30.3 0.3 0.3 0.3 Dry Effervescent granule 10 10 15 15 20 20 (malic acid44%, sodium bicarbonate 40%, sodium carbonate II, 10%, LAS 6%) Siliconeantifoam 0.5 0.5 0.5 0.5 0.5 0.5 Minors/inerts to 100%

The following granular laundry detergent compositions G to I ofparticular utility under European machine wash conditions were preparedin accord with the invention:

G H I LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS — 2.24 3.89 C25E3S —0.76 1.18 C45E7 3.25 — 5.0 C25E3 — 5.5 — QAS 0.8 2.0 2.0 STPP 19.7 — —Zeolite A — 19.5 19.5 Zeolite MAP 2.0 — — NaSKS-6/citric acid (79:21) —10.6 10.6 Carbonate I 4.7 19.3 18.6 Silicate 6.8 — — MA/AA 0.8 1.6 1.6CMC 0.2 0.4 0.4 PB4 5.0 12.7 — Percarbonate 5.0 — 12.7 TAED 0.5 3.1 — MnCatalyst 0.04 — — DTPMP 0.25 0.2 0.2 HEDP — 0.3 0.3 QEA 1 0.9 1.2 —Protease 0.26 0.85 0.85 Lipase 0.15 0.25 0.15 Cellulase 0.28 0.28 0.28Amylase 0.4 0.1 0.1 PVP 0.9 1.3 0.8 Photoactivated bleach (ppm) 15 ppm27 ppm 27 ppm Brightener 1 0.08 0.19 0.19 Brightener 2 — 0.04 0.04Perfume 0.3 0.3 0.3 Dry Fffervescent granules 10 15 5 (malic acid 40%,citric acid 6%, sodium bicarbonate 40%, sodium carbonate 14%) Siliconeantifoam 0.5 2.4 2.4 Minors/inerts to 100%

The following are high density and bleach-containing detergentformulations according to the present invention:

J K L Blown Powder Zeolite A 5.0 5.0 15.0 Sodium sulfate 0.0 5.0 0.0 LAS— 5.0 3.0 C45AS 3.0 2.0 4.0 QAS II — — 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.40.4 MA/AA 4.0 2.0 2.0 Dry Effervescent granules 20.0 5.0 (maleic acid30%, sodium bicarbonate 40%, sodium carbonate I 14%, PEG) Dry add DryEffervescent granules — 5.0 — (maleic acid 30%, sodium bicarbonate 40%,sodium carbonate II 14%, PEG 16%) Dry Effervescent granules — — 5.0(tartaric acid 30%, sodium bicarbonate 40%, sodium carbonate I 14%,TAE50 16%) Spray On (on particles) Encapsulated Perfume 0.3 0.3 0.3C25E3 — — 2.0 Dry additives QEA — — 0.5 Citrate 3.0 — 2.0 Bicarbonate —3.0 — Carbonate 8.0 10.0 5.0 NAC OBS 6.0 — — Manganese catalyst — — 0.3NOBS — 2.0 — PB1 or Percarbonate 14.0 7.0 — Polyethylene oxide of MW5,000,000 — — 0.2 Bentonite clay — — 10.0 Citric acid II — — 1.5Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate0.0 3.0 0.0 Balance 100.0 100.0 100.0 (Moisture and Miscellaneous)Density (g/liter) 850 850 850

The following are detergent formulations according to the presentinvention:

M N Dry Effervescent granules 10.0 — (maleic acid 30%, sodiumbicarbonate 40%, sodium carbonate I 14%, PEG) Dry Effervescent granules— 4.0 (malic acid 40% sodium bicarbonate 40%, sodium carbonate II 20%)Spray-on on dry effervescence particle C25E3 1.0 4.0 Perfume 0.5 0.5 DryAdds HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate/citric acid I — 2.0 Malic acid2.0 — NAC OBS 4.1 — TAED 0.8 — Percarbonate 20.0 5.0 SRP 1 0.3 0.3Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Amylase 0.6 0.6 QEA1.0 — Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 —Density (g/liter) 850 850

The following are high density detergent formulations according to thepresent invention:

O P R Agglomerate C45AS 11.0 14.0 5.0 QAS I 1.8 2.2 Zeolite A 15.0 6.015.0 Carbonate 4.0 8.0 5.0 AE5 5.0 TFAA II 5.0 MA/AA 4.0 2.0 2.0 CMC 0.50.5 0.5 DTPMP 0.4 0.4 0.4 Dry Effervescent granules 3.0 — 7.0 (malicacid 20%, sodium bicarbonate 20%, sodium carbonate II 20%, TAE50 10%TFAA II 30%) Spray On C25E3 1.0 4.0 4.0 C25E7 5.0 — — Perfume 0.5 0.50.5 Dry Adds HEDP 0.5 0.3 0.3 SKS 6 13.0 10.0 10.0 Citrate — 1.0 1.0Citric acid II 2.0 — — NAC OBS 4.1 6.2 6.2 TAED 0.8 1.0 1.0 Percarbonate20.0 20.0 20.0 SRP 1 0.3 0.3 0.3 Protease 1.4 1.4 1.4 Lipase 0.4 0.4 0.4Cellulase 0.6 0.6 0.6 Amylase 0.6 0.6 0.6 QEA 1.0 — — Silicone antifoam5.0 5.0 5.0 Brightener 1 0.2 0.2 0.2 Brightener 2 0.2 — — DryEffervescent granules 2.0 10.0 — (maleic acid 30% sodium bicarbonate30%, sodium carbonate I 10%,) Density (g/liter) 850 850 850

What is claimed is:
 1. A granular detergent composition comprising atleast one detergent active ingredient and from 3% to 25% by weight of adry effervescent granule, wherein the dry effervescent granule comprisesan acid wherein the acid is a mono or polycarboxylic acid selected fromthe group consisting of citric acid, adipic acid, glutaric acid, 3chetoglutaric acid, citramalic acid, maleic acid, fumaric acid, malicacid, succinic acid and malonic acid in their acidic forms, their mono-,di-, tri-salts form, their anhydrous and in their hydrated forms andmixtures thereof, a carbonate source selected from the group consistingof carbonate and bicarbonate, and a binder selected from the groupconsisting of cellulose derivatives, homo- and co-polymericpolycarboxylic acid and their salts, C₆-C₂₀ alkyl and alkylarylsulphonates and sulphates, polyvinylpyrrolidones with an averagemolecular weight of from about 12,000 to about 700,000, copolymers ofmaleic anhydride with ethylene, methylvinyl ether, methacrylic acid oracrylic acid, C₁₀-C₂₀ mono and diglycerol ethers, and mixtures thereof,wherein said acid, carbonate source and binder are in close physicalproximity and further wherein said dry effervescent granule is obtainedby pressure agglomeration of said acid, carbonate source and binder,characterized in that the granular detergent composition has anEffervescence Index (EI) of at least 10, the Effervescence Index (EI)being${EI} = {\frac{\left( {L \times S \times 100} \right)}{M} \times \left( {{NC}_{inter} + {NC}_{intra}} \right)}$

wherein L is the number of acidic groups of the acid having a pKa ofless than or equal to 6, S is (solubility in water of the acid ing/liter, at 25° C.)^(⅓), M is the molecular weight of the acid,NC_(inter) is the density of contact points between the carbonate sourceand acid which are separately present in the composition per mm³, andNC_(intra) is the weight fraction of the acid in said dry effervescentgranule x the weight fraction of the carbonate source in said dryeffervescent granule×12.
 2. A granular detergent composition accordingto claim 1 wherein the dry effervescent granules have a diameter size offrom 0.001 to 7 mm.
 3. A granular detergent composition according toclaim 1 wherein the dry effervescent granules have a bulk density offrom 500 g/l to 1200 g/l.
 4. A granular detergent composition accordingto claim 1 which comprises from 0.1% to 99% by weight of the total dryeffervescent granule of the acid or a mixture thereof, with the provisothat when citric acid is present its level is below 20% by weight of thetotal dry effervescent granule.
 5. A granular detergent compositionaccording to claim 1 which comprises from 0.1% to 99% by weight of thetotal dry effervescent granule of carbonate and/or bicarbonate.
 6. Agranular detergent composition according to claim 1 which comprises upto 50% by weight of the total dry effervescent granule of a binder or amixture thereof.
 7. A granular detergent composition according to claim1 which comprises an oxygen bleach, up to a level of 80% by weight ofthe total composition, bleach activator, up to a level of 30% by weightof the total composition.
 8. A granular detergent composition accordingto claim 1 which comprises at least a surfactant comprising a nonionicsurfactant or a mixture thereof up to a level of 50% by weight of thetotal composition.
 9. A granular detergent composition according toclaim 1 comprising the dry effervescent granule and a dry-added acid,selected from the group consisting of citric acid and malic acid and adry-added carbonate source.
 10. A granular detergent compositionaccording to claim 1 in the form of an extrudate or a tablet.
 11. Aprocess for manufacturing a dry effervescent granule according to claim1 wherein said process comprises the steps of: first mixing the acid,the carbonate source and the binder to form a mixture, then submittingthe mixture to a pressure agglomeration step to form an agglomeratemixture, and finally granulation of the agglomerate mixture in agranulation step.
 12. A process according to claim 11 wherein the bulkdensity of the dry effervescent granule having undergone said pressureagglomeration step is increased up to 200 g/l as compared to the bulkdensity of the resulting mixture comprising the acid and bicarbonateand/or carbonate, and the binder, before having undergone said pressureagglomeration step.
 13. A process according to claims 11, or whereinsaid pressure agglomeration step is a roller compaction step wherein theresulting mixture is forced between compaction rolls under pressure,whereafter the compacted mixture is granulated into dry effervescentgranules and optionally sieved.
 14. A process of soaking fabrics,wherein said fabrics are immersed in a soaking liquor comprising waterand an effective amount of a granular detergent composition according toclaim 1, for an effective period of time, then removed from said soakingliquor.